WO2018103276A1 - Thermosetting resin composition - Google Patents

Abstract

The present invention provides a thermosetting resin composition comprising an esterified dihydroxylphenyl phosphaphenanthrene. The thermosetting resin composition has the advantages of good thermal stability, heat and humidity resistance, toughness, a low dielectric constant and tangent of dielectric loss angle, a low water absorption, and a halogen-free flame-retardant effect, etc., as well as excellent processability. The invention also provides uses of the thermosetting resin composition in resin sheet, resin composite metal foil, prepreg, laminate, metal foil cladding laminate and printed circuit board.

Description

Thermosetting resin composition Technical field

The present invention relates to the field of polymer materials, and in particular to a thermosetting resin composition and a prepreg and printed circuit board using the same.

Background technique

Conventional printed circuit laminates usually use brominated flame retardants to achieve flame retardancy, especially with tetrabromobisphenol A epoxy resin, which has good flame retardancy, but it Hydrogen bromide gas is produced during combustion. Further, in recent years, carcinogens such as dioxins and dibenzofurans have been detected in combustion products of electrical and electronic equipment wastes containing halogens such as bromine and chlorine, and thus the application of brominated epoxy resins is limited. On July 1, 2006, the EU's two environmental protection directives, the Waste Electrical and Electronic Equipment Directive and the Directive on the Restriction of the Use of Certain Hazardous Substances in Electrical and Electronic Equipment, were officially implemented. Halogen-free flame-retardant copper clad laminates. Development has become a hot spot in the industry, and various copper foil laminate manufacturers have launched their own halogen-free flame-retardant copper clad laminates.

The introduction of a phosphorus-containing compound into the resin matrix of the copper clad laminate is the main technical route for the halogen-free flame retardant of the copper clad laminate. At present, phosphorus-based flame retardants widely used in the field of copper clad laminates are mainly classified into two types: reactive type and additive type. The reaction type is mainly a DOPO compound, and the phosphorus-containing epoxy resin and the phosphorus-containing phenolic resin are mainly used, and the phosphorus content is between 2% and 10%. However, in practical applications, it has been found that DOPO-based compounds have a large water absorption rate and poor dielectric properties, and the sheet has poor heat and humidity resistance. The addition type is mainly a phosphazene and a phosphonate compound, and the added flame retardant has a low flame retardancy efficiency, and it is necessary to add more amount to achieve the flame retardant requirement. At the same time, due to its lower melting point (generally lower than 150 ° C), it is easy to migrate to the surface of the sheet during the processing of the laminate, which affects the performance of the sheet.

In addition, for copper clad substrate materials, in order to meet PCB processing performance and terminal electronics The performance requirements of the product must have good dielectric properties, heat resistance and mechanical properties. At the same time, it should have good processing characteristics, high peel strength and excellent heat and humidity resistance.

DOPO-HQ is a reactive phosphorus-containing curing agent which can react with epoxy resin. However, since its reactive group is a phenolic hydroxyl group, it reacts with an epoxy resin to form a secondary hydroxyl group with a relatively large polarity. The dielectric properties of the cured product are poor. CN103965249A discloses a process for preparing an active ester of an alkyl group by using a phosphorus-containing phenanthrene and a use thereof, but the phosphorus-containing phenanthrene-linked alkyl group causes a slightly lower Tg when it is cured with an epoxy resin, so that it is on a high Tg copper clad plate. The use of this is limited. It is disclosed in CN105669760A that a non-active ester compound is synthesized by using a phosphorus-containing phenanthrene derivative and glycerin, and the engineering material can be flame-retarded in an added form, which also does not contribute to the Tg of the reinforcing material.

Summary of the invention

According to the study by the inventors, the esterified dihydroxyphenylphosphaphenanthrene is used as a curing agent for epoxy resin, and does not generate a secondary hydroxyl group with a large polarity when reacted with an epoxy resin, so that the dielectric properties of the system are better. Good, at the same time, it is a phosphorus-containing active curing agent. It is also used as a curing agent and has the effect of halogen-free flame retardant. It can be added in a small amount or without adding other flame retardants to make the sheet reach UL94 V-0. Halogen flame retardant effect.

Based on this, one of the objects of the present invention is to provide a thermosetting resin composition, and a prepreg and a laminate for printed circuit board using the same. The laminate for printed circuit board produced using the resin composition has high glass transition temperature, excellent dielectric properties, high heat resistance and moist heat resistance, excellent peel strength, and good processability, and can be realized. Halogen-free flame retardant, reaching UL94 V-0.

The present inventors conducted intensive studies to achieve the above object, and as a result, found that a composition obtained by appropriately mixing a halogen-free epoxy resin, an esterified bishydroxyphenylphosphaphenanthrene, and optionally other curing agents can be obtained. The above purpose.

That is, the present invention employs the following technical solution: a thermosetting resin composition comprising an epoxy resin and a curing agent, wherein the curing agent contains at least one esterified bishydroxyphenylphosphaphenanthrene.

The thermosetting resin composition of the present invention is a halogen-free thermosetting resin composition which uses esterified dihydroxyphenylphosphaphenanthrene as a curing agent for an epoxy resin. The active ester group as a reactive group has a high content, and can be cured with an epoxy resin to obtain a cured product having a high crosslinking density, and a material having good heat resistance and high Tg can be obtained; and the esterified dihydroxyphenylphosphonium is obtained. The phenanthrene structure has high symmetry, and the active ester unit in the molecule does not generate a secondary hydroxyl group having a large polarity after reacting with the epoxy resin, and the disadvantage of poor dielectric properties due to the secondary hydroxyl group having a large polarity can be eliminated. The dielectric property is excellent; the esterified dihydroxyphenylphosphaphenanthrene is an active ester, and the ester bond formed by the reaction with the epoxy has a low water absorption rate, thereby improving the disadvantage that the phosphorus-containing compound has poor moist heat resistance. In addition, the esterified dihydroxyphenylphosphaphene can have a halogen-free flame retardant effect, and UL94 V-0 flame retardant can be achieved with little or no additional flame retardant.

The present invention utilizes the highly symmetrical esterified dihydroxyphenylphosphaphenanthrene ester ester group to significantly improve the glass transition temperature and heat resistance of the prepreg prepared using the resin composition and the laminate for printed circuit boards. And it has excellent dielectric properties, low water absorption, good heat and humidity resistance, and good processability, and achieves halogen-free flame retardant, reaching UL94 V-0. Each component will be described in detail below.

According to the present invention, the esterified bishydroxyphenylphosphaphenanthrene has the structural formula shown in formula (I):

Wherein n ₁ is an integer from 1 to 20, such as 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20;

Wherein R _{1 is} selected from any one of the following groups:

Wherein Ar _{1 is} selected from any one of the following groups:

Wherein Ar _{2 is} selected from any one of the following groups:

Wherein n ₂ is an integer from 0 to 5, such as 0, 1, ₂ , 3, 4 or 5; n ₃ is an integer from 0 to 7, such as 0, 1, 2, 3, 4, 5, 6 or 7;

Wherein R ₂ is any one of a linear or branched alkyl group having 1 to 4 carbon atoms; and a linear or branched alkyl group having 1 to 4 carbon atoms may be, for example, a methyl group, an ethyl group or a propyl group. Any of a butyl group, a butyl group, an isopropyl group, an isobutyl group or a tert-butyl group.

The esterified bishydroxyphenylphosphaphenanthene of the present invention may have the following structural formula:

According to the present invention, the esterified bishydroxyphenylphosphaphene accounts for 20% to 50%, for example, 20%, 22%, 24%, 25 of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. %, 26%, 28%, 30%, 32%, 35%, 38%, 40%, 42%, 45%, 48% or 50%, and the specific point value between the above values, limited by space and out For the sake of brevity, the present invention is no longer exhaustive of the specific point values included in the scope.

According to the present invention, the epoxy resin accounts for 30 to 60%, for example, 30%, 32%, 34%, 35%, 36%, 38%, of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. 40%, 42%, 45%, 48%, 50%, 52%, 55%, 58% or 60%, and the specific point value between the above values, limited by space and for the sake of concise consideration, the present invention is no longer Exhaustive enumeration of specific point values included in the stated range.

In the present invention, the epoxy resin is a halogen-free epoxy resin, which means an epoxy resin having two or more epoxy groups in one molecule, and is selected from glycidyl ethers and glycidyl esters. Any one or a mixture of at least two of a glycidylamine, an alicyclic epoxy resin, an epoxidized olefin, a hyacinol epoxy resin or an imide epoxy resin.

Preferably, the glycidyl ethers include bisphenol A epoxy resin, bisphenol F epoxy resin, o-cresol novolac epoxy resin, bisphenol A novolac epoxy resin, and trisphenol novolac epoxy resin. Any one or a mixture of at least two of a dicyclopentadiene novolac epoxy resin, a biphenyl type novolac epoxy resin, an alkylbenzene type novolac epoxy resin or a naphthol type novolac epoxy resin. The above epoxy resins are all halogen-free epoxy resins.

Preferably, the glycidyl ether is selected from the group consisting of epoxy resins having the following structure:

R₃为氢原子、取代或未取代的含碳数1～5的直链烷基或支链烷基中的任意一种。Wherein Z ₁ , Z ₂ and Z ₃ are each independently selected from

R ₃ is a hydrogen atom, a substituted or unsubstituted linear alkyl group having 1 to 5 carbon atoms or a branched alkyl group.

中的任意一种，n₃为1～10的任意整数，例如1、2、3、4、5、6、7、8、9或10，R₄选自氢原子、含碳数1～5的直链烷基或支链烷基中的任意一种；例如可以是甲基、乙基、丙基、丁基、戊基、异丙基、异丁基、叔丁基或异戊基中的任意一种。Y ₁ and Y ₂ are each independently selected from -CH ₂ -,

Any one of them, n ₃ is an arbitrary integer of 1 to 10, for example, 1, 2, 3, ₄ , 5, 6, 7, 8, 9, or 10, and R _{4 is} selected from a hydrogen atom and has a carbon number of 1 to 5 Any one of a linear alkyl group or a branched alkyl group; for example, it may be a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group, an isobutyl group, a t-butyl group or an isopentyl group. Any of them.

Preferably, the glycidylamine is selected from the group consisting of triglycidyl-p-aminophenol, triglycidyl trimer isocyanate, tetraglycidyldiaminodimethylenebenzene, tetraglycidyl-4,4' -diaminodiphenylmethane, tetraglycidyl-3,4'-diaminodiphenyl ether, tetraglycidyl-4,4'-diaminodiphenyl ether or tetraglycidyl-1,3 Any one or a mixture of at least two of diaminomethylcyclohexane.

The halogen-free thermosetting resin composition of the present invention employs the halogen-free epoxy resin having the specific molecular structure described above, which has high functionality and good dielectric properties, and has a high Tg of cured product and low water absorption.

According to the present invention, the curing agent may further comprise a cyanate resin and/or a bismaleimide-triazine resin; wherein the cyanate resin has the following structure:

中的任意一种或至少两种的混合物；R₅、R₆、R₇、R₈、R₉、R₁₀、R₁₁或R₁₂各自独立地选自氢原子、取代或未取代的含碳数1～4的直链烷基或支链烷基中的任意一种，例如可以是甲基、乙基、丙基、丁基、异丙基、异丁基或叔丁基中的任意一种。 Wherein R ₁₃ is -CH ₂ -,

Any one or a mixture of at least two; R ₅ , R ₆ , R ₇ , R ₈ , R ₉ , R ₁₀ , R ₁₁ or R ₁₂ are each independently selected from a hydrogen atom, a substituted or unsubstituted carbonaceous Any one of a linear alkyl group or a branched alkyl group having 1 to 4 may be, for example, any one of a methyl group, an ethyl group, a propyl group, a butyl group, an isopropyl group, an isobutyl group or a t-butyl group. Kind.

Preferably, the cyanate resin is selected from the group consisting of 2,2-bis(4-cyanooxyphenyl)propane, bis(4-cyanooxyphenyl)ethane, bis(3,5-dimethyl- 4-cyanooxyphenyl)methane, 2,2-bis(4-cyanooxyphenyl)-1,1,1,3,3,3-hexafluoropropane, α,α'-bis(4- Cyanooxyphenyl)-m-isopropylbenzene, cyclopentadiene cyanate, phenol novolac cyanate, cresol novolac cyanate, 2,2-bis(4-cyanooxybenzene) Propane prepolymer, bis(4-cyanooxyphenyl)ethane prepolymer, bis(3,5-dimethyl-4-cyanooxyphenyl)methane prepolymer, 2,2- Bis(4-cyanooxyphenyl)-1,1,1,3,3,3-hexafluoropropane prepolymer, α,α'-bis(4-cyanooxyphenyl)-diisopropylidene Any one or a mixture of at least two of a benzene prepolymer, a dicyclopentadiene type cyanate prepolymer, a phenol novolac type cyanate prepolymer or a cresol novolac type cyanate prepolymer, Preferred is 2,2-bis(4-cyanooxyphenyl)propane, α,α'-bis(4-cyanooxyphenyl)-m-isopropylidenebenzene, bis(3,5-dimethyl 4-cyanooxyphenyl)methane, 2,2-bis(4-cyanooxyphenyl)propane prepolymer, α,α'- Any one or at least two of (4-cyanooxyphenyl)-m-diisopropylbenzene prepolymer or bis(3,5-dimethyl-4-cyanooxyphenyl)methane prepolymer Kind of mixture.

According to the present invention, the cyanate resin and/or bismaleimide-triazine resin accounts for 0% to 50%, for example 0%, of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. 2%, 4%, 5%, 8%, 10%, 12%, 14%, 15%, 17%, 20%, 22%, 25%, 30%, 32%, 35%, 37%, 39% 40%, 42%, 45%, 48%, or 50%, and the specific point values between the above values are limited to the length and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the range.

According to the present invention, the curing agent may further comprise an SMA resin; the SMA resin means a styrene-maleic anhydride resin which can be obtained by copolymerization of styrene and maleic anhydride in a ratio of from 1:1 to 8:1.

According to the present invention, the SMA resin accounts for 0% to 40%, for example, 0%, 2%, 4%, 5%, 8%, 10%, of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. 12%, 14%, 15%, 17%, 20%, 22%, 25%, 30%, 32%, 35%, 37%, 39% or 40%, and the specific value between the above values is limited For the sake of brevity and conciseness, the present invention is no longer exhaustively enumerated. The specific point value included.

According to the present invention, the curing agent may further comprise a phenolic resin; the phenolic resin is a phosphorus-containing or phosphorus-free phenolic resin, which is a phenolic resin well known in the art, and is not particularly limited in the present invention.

According to the present invention, the phenolic resin accounts for 0% to 20%, such as 0%, 2%, 4%, 5%, 8%, 10%, of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. 12%, 14%, 15%, 17%, or 20%, and the specific point values between the above values are limited, and for the sake of brevity, the present invention will not exhaustively enumerate the specific point values included in the range.

The thermosetting resin composition of the present invention, the organic solid content is 100 parts by weight, and specifically comprises: esterified bishydroxyphenylphosphaphenanthene: 20-50 parts by weight; halogen-free epoxy resin: 30-60 weight Parts; cyanate resin and/or bismaleimide-triazine resin: 0 to 50 parts by weight; SMA resin: 0 to 40 parts by weight; phenol resin: 0 to 20 parts by weight.

The "total weight of the epoxy resin and the curing agent in the thermosetting resin composition" referred to in the present invention means the total weight of the components participating in the crosslinking polymerization reaction, wherein the curing agent means curing the epoxy resin Effect of esterified bishydroxyphenylphosphaphenanthene and optionally cyanate resin and/or bismaleimide-triazine resin, SMA resin or phenolic resin, which does not contain fillers, accelerators and flame retardants Components such as agents.

The thermosetting resin composition of the present invention may further comprise an organic halogen-free flame retardant, and the organic halogen-free flame retardant may specifically be selected from the group consisting of phosphorus-containing flame retardants.

According to the present invention, the phosphorus-containing flame retardant may be selected from the group consisting of tris(2,6-dimethylphenyl)phosphine, 10-(2,5-dihydroxyphenyl)-9,10-dihydro-9- Oxa-10-phosphaphenanthrene-10-oxide, 2,6-bis(2,6-dimethylphenyl)phosphinobenzene, 10-phenyl-9,10-dihydro-9-oxa- Any one or a mixture of at least two of 10-phosphaphenanthrene-10-oxide, phenoxyphosphazene compound, phosphate, polyphosphate, polyphosphonate or phosphonate-carbonate copolymer.

In the present invention, the total amount of the epoxy resin and the curing agent in the thermosetting resin composition is 100 parts by weight, and the content of the organic halogen-free flame retardant is 0 to 15 parts by weight, that is, according to the esterified double Hydroxyphenyl phosphate The sum of the addition amount of the phenanthrene, the epoxy resin, and the cyanate resin, the SMA resin, and the phenol resin to be added is 100 parts by weight, and the organic halogen-free flame retardant is added in an amount of 0 to 15 parts by weight, for example, 1 part by weight. Parts, 3 parts by weight, 5 parts by weight, 6 parts by weight, 8 parts by weight, 9 parts by weight, 10 parts by weight, 11 parts by weight, 12 parts by weight, 13 parts by weight or 15 parts by weight, and specific points between the above values Values, limited by length and for the sake of brevity, the present invention is no longer exhaustive of the specific point values included in the scope.

The halogen-free thermosetting resin composition of the present invention may further comprise a curing accelerator.

Preferably, the curing accelerator comprises an organic metal salt and any one or at least two selected from the group consisting of an imidazole compound, a derivative of an imidazole compound, a piperidine compound, a pyridine compound, a Lewis acid or a triphenylphosphine. Kind of mixture.

Preferably, the organometallic salt in the curing accelerator comprises any one of a metal octoate, a metal isooctanoate, a metal acetylacetonate, a metal naphthenate, a metal salicylate or a metal stearate. Or a mixture of at least two, wherein the metal is selected from any one or a mixture of at least two of zinc, copper, iron, tin, cobalt or aluminum.

Preferably, the imidazole compound is any one of 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole or 2-undecylimidazole or a mixture of at least two .

Preferably, the piperidine compound is 2,3-diaminopiperidine, 2,5-diaminopiperidine, 2,6-diaminopiperidine, 2-amino-3-methylpiperidine, 2- Any one of amino-4-methylpiperidine, 2-amino-3-nitropiperidine, 2-amino-5-nitropiperidine or 2-amino-4,4-dimethylpiperidine or a mixture of at least two.

Preferably, the pyridine compound is any one or a mixture of at least two of 4-dimethylaminopyridine, 2-aminopyridine, 3-aminopyridine or 4-aminopyridine.

Preferably, the addition of the curing accelerator is based on 100 parts by weight of the sum of the esterified bishydroxyphenylphosphaphenanthrene, epoxy resin, and possibly added cyanate resin, SMA resin, and phenol resin. The amount is 0.01 to 1 part by weight, for example, 0.01 parts by weight, 0.025 parts by weight, 0.05 parts by weight, 0.07 parts by weight, 0.085 parts by weight, 0.1 parts by weight, 0.3 parts by weight, 0.5 parts by weight, 0.8 parts by weight, 0.9 parts by weight or 1 part by weight, preferably 0.025 to 0.85 parts by weight.

The halogen-free thermosetting resin composition of the present invention may further comprise a filler.

Preferably, the filler is selected from the group consisting of organic or inorganic fillers, preferably inorganic fillers, further preferably surface treated inorganic fillers, most preferably surface treated silica.

Preferably, the surface treated surface treatment agent is selected from any one or a mixture of at least two of a silane coupling agent, a silicone oligomer or a titanate coupling agent.

Preferably, the surface treatment agent is used in an amount of 0.1 to 5 parts by weight, preferably 0.5 to 3 parts by weight, more preferably 0.75 to 2 parts by weight, based on 100 parts by weight of the inorganic filler.

Preferably, the inorganic filler is selected from any one or a mixture of at least two of a non-metal oxide, a metal nitride, a non-metal nitride, an inorganic hydrate, an inorganic salt, a metal hydrate or an inorganic phosphorus, preferably molten. Silica, crystalline silica, spherical silica, hollow silica, aluminum hydroxide, alumina, talc, aluminum nitride, boron nitride, silicon carbide, barium sulfate, barium titanate, titanium Any one or a mixture of at least two of acid strontium, calcium carbonate, calcium silicate or mica.

Preferably, the organic filler is selected from any one or a mixture of at least two of polytetrafluoroethylene powder, polyphenylene sulfide or polyethersulfone powder.

Preferably, the filler has a median particle diameter of from 0.01 to 50 μm, preferably from 0.01 to 20 μm, further preferably from 0.1 to 10 μm.

Preferably, the filler is added in an amount of 100 parts by weight based on 100 parts by weight of the combined amount of the esterified bishydroxyphenylphosphaphenanthrene, the epoxy resin, and the cyanate resin, the SMA resin, and the phenol resin which may be added. 5 to 300 parts by weight, preferably 5 to 200 parts by weight, more preferably 5 to 150 parts by weight.

The term "comprising" as used in the present invention means that it may include other components in addition to the components, and these other components impart different characteristics to the halogen-free thermosetting resin composition. In addition to the above, the present invention The "contains" can also be replaced by a closed "for" or "consisting of".

For example, the halogen-free thermosetting resin composition may further contain various additives, and specific examples thereof include an antioxidant, a heat stabilizer, an antistatic agent, an ultraviolet absorber, a pigment, a colorant, a lubricant, and the like. These additives may be used singly or in combination of two or more.

The preparation method of the halogen-free thermosetting resin composition of the present invention is a conventional technical means in the art, which is: firstly, the solid matter is put in, then the liquid solvent is added, and the mixture is stirred until the solid matter is completely dissolved, and then the liquid resin is added. Accelerator, continue to stir evenly.

The solvent in the present invention is not particularly limited, and specific examples thereof include alcohols such as methanol, ethanol, and butanol, ethyl cellosolve, butyl cellosolve, ethylene glycol methyl ether, carbitol, and butyl. Ethers such as carbitol, ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone, cyclohexanone; aromatic hydrocarbons such as toluene and xylene; esters such as ethyl acetate and ethoxyethyl acetate a nitrogen-containing solvent such as N,N-dimethylformamide or N,N-dimethylacetamide. The above solvents may be used singly or in combination of two or more. Preference is given to ketones such as acetone, methyl ethyl ketone, methyl ethyl ketone and cyclohexanone. The amount of the solvent to be added is selected by those skilled in the art based on his own experience, so that the resin glue can reach a viscosity suitable for use.

The prepreg of the present invention comprises a reinforcing material and a halogen-free thermosetting resin composition as described above which is impregnated and adhered to the reinforcing material after drying, and the reinforcing material to be used is not particularly limited and may be an organic fiber, an inorganic fiber woven fabric or Non-woven fabric. The organic fiber may be selected from aramid nonwoven fabric, and the inorganic fiber woven fabric may be E-glass fabric, D-glass fabric, S-glass fabric, T-glass fabric, NE-glass fabric. Or quartz cloth. The thickness of the reinforcing material is not particularly limited, and the thickness of the woven fabric and the nonwoven fabric is preferably 0.01 to 0.2 mm, and preferably the fiber-opening treatment and the silane coupling agent are considered. The surface treatment, in order to provide good water resistance and heat resistance, the silane coupling agent is preferably any one or at least two of an epoxy silane coupling agent, an amino silane coupling agent or a vinyl silane coupling agent. Kind of mixture. The reinforcing material is impregnated with the above halogen-free thermosetting resin composition at 100 to 250 ° C The prepreg is obtained by baking for 1 to 15 minutes.

The laminate for printed circuit of the present invention comprises a laminate prepared by bonding together one or two or more prepregs by heat and pressure, and a metal foil bonded to one or both sides of the laminate. . The laminate is obtained by curing in a hot press at a curing temperature of 150 to 250 ° C and a curing pressure of 10 to 60 kg/cm ² . The metal foil is copper foil, nickel foil, aluminum foil, SUS foil, etc., and the material thereof is not limited.

Compared with the prior art, the present invention has at least the following beneficial effects:

The prepreg and the printed circuit board made of the halogen-free thermosetting resin composition provided by the invention have a glass transition temperature of up to 245 ° C; excellent dielectric properties, and the water absorption rate is controlled in the range of 0.07-0.1% Internal; high heat resistance; excellent heat and humidity resistance and good processability; excellent flame retardant efficiency, UL content of 1.5% can reach UL94 V-0.

detailed description

The technical solution of the present invention will be further described below by way of specific embodiments.

The following is a specific embodiment of the embodiments of the present invention. It should be noted that those skilled in the art can make some improvements and refinements without departing from the principles of the embodiments of the present invention. And retouching is also considered to be the scope of protection of the embodiments of the present invention.

The embodiments of the present invention are further described below in various embodiments. The embodiments of the present invention are not limited to the specific embodiments below. Modifications can be made as appropriate without departing from the scope of the claims.

1. Synthesis of P-AE1

320 g of ODOPB, 213 g of p-benzoic acid chloride and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer while introducing nitrogen gas, followed by raising the temperature to 30 ° C, and reacting at this temperature for 4 hours. Then, 15 g of phenol was further added to the reaction system, and the reaction was also carried out at this temperature for 2 hours. The product was cooled to room temperature and then a 5% sodium carbonate solution was added and stirred vigorously, filtered, washed with water and dried to give a product. The number is P-AE1.

Where n ₁ = 20.

2. Synthesis of P-AE2

370 g of 10-(2,5-dihydroxynaphthyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, 243.6 g of m-chlorobenzoyl chloride and 1500 g of pyridine in a stirrer The condensing reflux tube and the four-necked flask of the thermometer were stirred while introducing nitrogen gas, and then the temperature was raised to 30 ° C, and the reaction was carried out at this temperature for 4 hours. Then, 50 g of 2,6-dimethylphenol was further added to the reaction system, and the reaction was also carried out at this temperature for 2 hours. The product was cooled to room temperature and then a 5% sodium carbonate solution was added and stirred vigorously, filtered, washed with water and dried to give product g, numbered P-AE2.

Where n ₁ =10.

3. Synthesis of P-AE3

370 g of 10-(2,5-dihydroxynaphthyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide, 285 g of p-chlorobenzoyl chloride and 1500 g of pyridine were placed in a stirrer, The condensing reflux tube and the four-necked flask of the thermometer were stirred while introducing nitrogen gas, and then the temperature was raised to 30 ° C, and the reaction was carried out at this temperature for 4 hours. Then, 120 g of p-tert-butylphenol was further added to the reaction system, and the reaction was also carried out at this temperature for 2 hours. The product was cooled to room temperature and then a 5% sodium carbonate solution was added and stirred vigorously, filtered, washed with water and dried to give the product, numbered P-AE3.

Where n ₁ = 5.

4. Synthesis of P-AE4

320 g of ODOPB, 418 g of diphenyldichloride chloride and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer while introducing nitrogen gas, followed by raising the temperature to 30 ° C, and reacting at this temperature for 4 hours. Then, 216 g of p-methylphenol was further added to the reaction system, and the reaction was also carried out at this temperature for 2 hours. The product was cooled to room temperature and then a 5% sodium carbonate solution was added and stirred vigorously, filtered, washed with water and dried to give a product, numbered P-AE4.

Where n ₁ = 3.

5. Synthesis of P-AE5

370 g of bis(4-hydroxyphenyl)phosphine oxide, 506 g of 2,6-naphthalenediyl chloride and 1500 g of pyridine were stirred in a four-necked flask equipped with a stirrer, a condensing reflux tube, and a thermometer while introducing nitrogen gas and then raising the temperature. At 30 ° C, react at this temperature for 4 h. Then, 244 g of 2,6-dimethylphenol was further added to the reaction system, and the reaction was also carried out at this temperature for 2 hours. The product was cooled to room temperature and then a 5% sodium carbonate solution was added and stirred vigorously, filtered, washed with water and dried to give a product, numbered P-AE5.

Where n ₁ =1.

P-AE (esterified bishydroxyphosphaphenanthrene), halogen-free epoxy resin and curing accelerator, halogen-free flame retardant, filler are uniformly mixed in a certain ratio in the solvent, and the solid content of the glue is controlled to be 65%. The above glue is impregnated with a 2116 glass fiber cloth, and the appropriate thickness is controlled. Then, the prepreg is prepared by baking in an oven at 115 to 175 ° C for 2 to 15 minutes, and then several prepregs are stacked and stacked on both sides. The upper 18μRTF copper foil is made into a copper clad laminate under the conditions of a curing temperature of 170-250 ° C, a curing pressure of 25-60 kg/cm ² and a curing time of 60-300 min.

Examples 1-20 and Comparative Examples 1-8 relate to materials and grade information as follows:

(A)

P-AE1: Self-made esterified modified bishydroxyphenylphosphine phenanthrene

Where n ₁ = 20.

P-AE2: Self-made esterified modified bishydroxyphenylphosphine phenanthrene

Where n ₁ =10.

P-AE3: Self-made esterified modified bishydroxyphenylphosphine phenanthrene

Where n ₁ = 5.

P-AE4: Self-made esterified modified bishydroxyphenylphosphine phenanthrene

Where n ₁ = 3.

P-AE5: Self-made esterified modified bishydroxyphenylphosphine phenanthrene

Where n ₁ =1.

ODOPB: 10-(2,5-dihydroxyphenyl)-10-hydro-9-oxa-10-phosphaphenanthrene-10-oxide

FRX-3001:

(B) Cyanate ester

CY-40: Wuqiao resin factory, DCPD type cyanate resin

PT60S: LONCZ, phenolic cyanate resin

CE01PS: Jiangsu Tianqi, bisphenol A type cyanate resin

CE01MO: Jiangsu Tianqi, bisphenol A type cyanate resin

(C) epoxy resin

HP-7200HHH: DIC, DCPD type epoxy resin, epoxy equivalent 288

HP-7200H-75M: DIC, DCPD type epoxy resin, epoxy equivalent 280

HP-6000: DIC, epoxy resin, epoxy equivalent 250

HP-9900: DIC, naphthol type epoxy resin, epoxy equivalent 274

NC-3000H: Nippon Chemical, Biphenyl Epoxy Resin, Epoxy Equivalent 294

SKE-1: Shankote, special epoxy resin, epoxy equivalent 120

SKE-3: Shankote, special epoxy resin, epoxy equivalent 120

(D) phenolic resin

DOW92741: Phosphorus-containing phenolic, Dow Chemical

SEB-0904PM60: Phosphorus phenolic, SHIN-A

SHN-1655TM65: Phosphorus-containing phenolic, SHIN-A

2812: Linear phenolic resin, MOMENTIVE (Korea)

(E) phosphorus-containing flame retardant

SPB-100: Otsuka Chemical, phosphazene flame retardant, phosphorus content 13.4%

(F)SMA

1000P: SMA, styrene-maleic anhydride copolymer, Sartomer

EF40: SMA, styrene-maleic anhydride copolymer, Sartomer

EF60: SMA, styrene-maleic anhydride copolymer, Sartomer

EF80: SMA, styrene-maleic anhydride copolymer, Sartomer

(G) accelerator

2E4MZ: 2-ethyl-4-methylimidazole, the formation of four countries

DMAP: 4-dimethylaminopyridine, Guangrong Chemical

BICAT Z: Zinc Isooctanoate, The Shepherd Chemical Company

(H) filler

Fused silica (average particle size 0.2 to 10 μm, purity 99% or more)

Tables 1-4 are the formulation compositions and physical property data of Examples 1 to 20, Table 5, Comparative Examples 1 to 8.

Table 1

Table 2

Example 6 Example 7 Example 8 Example 9 Example 10 P-AE2 20 20 20 20 50 CE01MO 50 CEO1PS 40 CY-40 30 PT-60S 20 10 HP-6000 50 NC-3000H 60 SKE-1 30 SKE-3 40 40 SPB-100 3 5 10 15 0 DMAP 0.01 0.08 0.1 1 0.3 Spherical silicon 100 25 25 25 5 P% 1.50% 1.73% 2.26% 2.74% 2.87% Tg(DMA)/°C 245 235 210 195 198 Dk (10GHz) 4.2 3.8 3.8 3.9 3.8 Df (10GHz) 0.0072 0.072 0.075 0.0078 0.008 Water absorption /% 0.05 0.07 0.07 0.07 0.1 PCT/6h OOO OOO OOO OOO OOO T288/min >60 >60 >60 >60 >60 Difficult to burn V-0 V-0 V-0 V-0 V-0

table 3

Table 4

Example 16 Example 17 Example 18 Example 19 Example 20 P-AE1 20 P-AE2 30 P-AE3 40 P-AE4 50 P-AE5 50 92741 10 SEB-0904PM60 10 SHN-1655TM65 5 20 2812 10 5 5 5 HP-7200HHH 45 HP-6000 50 HP-9900 55 NC-3000H 60 2E4MZ 0.1 0.1 0.1 0.1 0.1 Spherical silicon 25 25 25 25 25 P% 2.22% 2.72% 2.45% 2.31% 2.99% Tg(DMA)/°C 180 185 180 190 195 Dk (10GHz) 3.8 3.8 3.8 3.8 3.8 Df (10GHz) 0.008 0.0075 0.0075 0.0085 0.007 Water absorption /% 0.08 0.08 0.08 0.08 0.085

PCT/6h OOO OOO OOO OOO OOO T288/min >60 >60 >60 >60 >60 Difficult to burn V-0 V-0 V-0 V-0 V-0

table 5

Supplementary description of the PCT/6h performance icon: × is a layered burst board, and O is a layered burst board.

The test methods for the above characteristics are as follows:

(1) Glass transition temperature (T _g ): Measured according to the DMA test method specified in IPC-TM-650 2.4.24 using a DMA test.

(2) Dielectric constant and dielectric loss factor: tested according to the SPDR method.

(3) Evaluation of heat and humidity resistance (PCT): After etching the copper foil on the surface of the copper clad laminate, the substrate was evaluated; the substrate was placed in a pressure cooker, treated at 120 ° C, 105 KPa for 6 hours, and then immersed in a tin furnace at 288 ° C. Record the corresponding time when the substrate is delaminated; when the substrate is in the tin furnace for more than 5 minutes, it has not appeared. The evaluation can be ended when foaming or delamination.

(4) T288: Determined by TMA instrument according to the T300 test method specified in IPC-TM-650 2.4.24.1.

(5) Water absorption: The measurement was carried out in accordance with the water absorption test method specified in IPC-TM-650 2.6.2.1.

(6) Flame retardancy: It was carried out in accordance with the UL 94 standard method.

From the comparison of the data in Table 1-5, the following points can be seen:

Comparative Example 1 and Example 4, the copper clad laminate prepared by using ODOBP and the halogen-free epoxy resin in Comparative Example 1 has poor dielectric properties, poor moist heat resistance, high water absorption, and low Tg; Comparative Example 2 and Examples 9 comparison, the copper clad laminate prepared by using ODOBP and cyanate resin and halogen-free epoxy resin in Comparative Example 2 has poor dielectric properties, high water absorption, poor moist heat resistance and low Tg; Comparative Example 3 and Example 13 In comparison, the copper clad laminate prepared by using ODOBP and SMA resin and halogen-free epoxy resin in Comparative Example 3 has poor dielectric properties, high water absorption, and poor heat and humidity resistance; Comparative Example 4 is compared with Example 17, in Comparative Example 4 The copper clad laminate prepared by using ODOBP and phenolic resin and halogen-free epoxy resin has poor dielectric properties, high water absorption, poor heat resistance and moist heat resistance, and low Tg; Comparative Example 5 is compared with Example 4, Comparative Example 5 The FRX3001 was used to cure the halogen-free epoxy resin. Under the same conditions, the FRX3001 was poor in reactivity and the OH ^- content was low, so that the copper-clad laminate could not be produced. In Comparative Example 6 and Comparative Example 9, FRX3001 and cyanate were used in Comparative Example 6. Dielectric properties of copper clad laminates made of resin and halogen-free epoxy resin Difference, high water absorption, heat resistance and moist heat resistance and the difference between a low Tg, poor flame retardancy.

Further, comparing Comparative Example 7 with Example 9, it is understood that when the content of Comparative Example 7 is higher than that of the esterified bishydroxyphenylphosphaphene in Example 9, the heat resistance of the copper clad laminate produced is The heat resistance and the moist heat resistance are poor, the Tg is low, and the flame retardancy is poor. Comparing Comparative Example 8 with Example 9, it is understood that the content of the esterified bishydroxyphenylphosphonium in Example 8 is lower than that in Example 9. When the curing agent is insufficient, the sheet cannot be formed.

From the above results, it can be seen that by replacing ODOBP and FRX with the esterified bishydroxyphenylphosphaphene of the present invention, a prepreg made of a halogen-free epoxy resin or the like, and a laminate for a printed circuit board, It has a glass transition temperature of up to 245 ° C; excellent dielectric properties, water absorption controlled in the range of 0.07-0.1%; high heat resistance; excellent heat and humidity resistance and good processability; excellent flame retardant efficiency, UL94 V-0 can be achieved with a P content of 1.5%.

As described above, the prepreg and the printed circuit board laminate made of the halogen-free thermosetting resin composition provided by the present invention have a high glass transition temperature and excellent dielectric properties as compared with a general laminate. Low water absorption, high heat resistance, excellent heat and humidity resistance, and good processability, and can achieve halogen-free flame retardant, reaching UL94 V-0.

The above is only a preferred embodiment of the present invention, and various other changes and modifications can be made in accordance with the technical solutions and technical concept of the present invention, and all such changes and modifications will be made to those skilled in the art. Modifications are intended to fall within the scope of the claims of the present invention.

Claims (7)

A thermosetting resin composition comprising an epoxy resin and a curing agent, wherein the curing agent comprises at least one esterified bishydroxyphenylphosphaphenanthrene, and the structural formula is as shown in formula (I);

Wherein n ₁ is an integer of 1-20; Wherein R _{1 is} selected from any one of the following groups:

Wherein Ar _{1 is} selected from any one of the following groups:

Wherein Ar _{2 is} selected from any one of the following groups:

Wherein n ₂ is an integer of 0 to 5; and n ₃ is an integer of 0 to 7; Wherein R ₂ is any one of a linear or branched alkyl group having 1 to 4 carbon atoms; The esterified bishydroxyphenylphosphaphene accounts for 20% to 50% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition; The epoxy resin accounts for the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. 30% to 60%. The thermosetting resin composition according to claim 1, wherein the curing agent further comprises a cyanate resin and/or a bismaleimide-triazine resin; Preferably, the cyanate resin and/or bismaleimide-triazine resin accounts for 0% to 50% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. The thermosetting resin composition according to claim 1 or 2, wherein the curing agent further comprises an SMA resin; Preferably, the SMA resin is obtained by copolymerizing styrene and maleic anhydride in a ratio of 1:1 to 8:1; Preferably, the SMA resin accounts for 0% to 40% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 3, wherein the curing agent further comprises a phenol resin; Preferably, the phenolic resin accounts for 0% to 20% of the total weight of the epoxy resin and the curing agent in the thermosetting resin composition. The thermosetting resin composition according to any one of claims 1 to 4, wherein the thermosetting resin composition further comprises an organic halogen-free flame retardant; Preferably, the organic halogen-free flame retardant is a phosphorus-containing flame retardant; Preferably, the total amount of the epoxy resin and the curing agent in the thermosetting resin composition is from 0 to 15 parts by weight based on 100 parts by weight of the organic halogen-free flame retardant. The thermosetting resin composition according to any one of claims 1 to 5, wherein the thermosetting resin composition further contains a filler and/or an accelerator. Use of the thermosetting resin composition according to any one of claims 1 to 6 in a resin sheet, a resin composite metal foil, a prepreg, a laminate, a metal foil-clad laminate or a printed wiring board.